Investigation of sandwiched gadolinium(III) complexes with tungstosilicates as potential MRI contrast agents

Two gadolinium-sandwiched complexes with tungstosilicates, K-13[Gd(SiW11O39)(2)] (Gd(SiW11)(2)) and K11H6[Gd2O3(SiW9O34)(2)] (Gd-3(SiW9)(2)), have been investigated by in vitro and in vivo experiments as potential contrast agents for magnetic resonance imaging (MRI). T-1-relaxivity of Gd(SiW11)(2)was 6.59 mM(-1) . s(-1) in aqueous solution and 6.85 mM(-1) . s(-1) in 0.725 mmol . L-1 bovine serum albumin solution at 25degreesC and 9.39 T, respectively. The corresponding T-1-relaxivity of Gd-3(SiW9)(2) was 12.6 and 19.3 mM(-1) . s(-1) per Gd, respectively. MRI for Sprague-Dawley rats showed longer and more remarkable enhancement in rat liver after i.v. injection of these two complexes: 39.4 +/- 3.9% and 57.4 +/- 11.6% within the first 30 min after injection, 31.2 +/- 2.6% and 39.9 +/- 7.6% in the next 60 min for Gd(SiW11)(2) and Gd-3(SiW9)(2) at doses of 0.081 and 0.084 mmol Gd/kg, respectively. Our preliminary in vitro and in vivo study indicates that Gd(SiW11)(2) and Gd-3(SiW9)(2) are favorable candidates for hepatic contrast agents for MRI. However, the two complexes exhibit higher acute toxicity and need to be modified and studied further before clinical use.

Highly efficient green phosphorescent organic light-emitting diodes based on Cu-I complexes

Mononuclear Cu-I complexes with mixed ligands are used to fabricate green phosphorescent organic light-emitting diodes. The electroluminescence (EL) maximum at 524 nm coincides well with its photoluminescent (PL) spectrum in poly(methyl methacrylate) film (see Figure). A maximum current efficiency of 10.5 cd A(-1) at 105 cd m(-2) and a maximum brightness up to 1663 cd m(-2) are

Syntheses and characterization of half-sandwich zirconium complexes with dichalcogenolate o-carborane ligands

Metallocene complex (Cp2ZrCl2)-Zr-tt (Cp-tt = eta(5)-1,3-(Bu2C5H3)-Bu-t) (1) has been prepared from the reaction of LiCptt with ZrCl4 in good yield. Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands [Li(THF)(4)][(CpZr)-Zr-tt(E2C2B10H10)(2)] (E = S, 2a; E = Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X-ray analyses. In complex 2a, the Zr(IV) ion is eta(5)-bound to one 1,3-di-tert-cyclopentadienyl ring and a-bound to four mu(2)-sulfur atoms of two dithio-carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.

Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

Sequential deprotonation of meso-(p-hydroxyphenyl)porphyrins in DMF: From hyperporphyrins to sodium porphyrin complexes

Sequential deprotonations of meso-(p-hydroxyphenyl)porphyrins (p-OHTPPH2) in DMF + H2O (V/V = 1:1) mixture have been verified to result in the appearance of hyperporphyrin spectra. However, when the deprotonations of these p-OHTPPH2 are carried out in DMF, the spectral changes differ considerably from those in the mixture mentioned above. At low [OH-], the optical spectra in the visible region are still considered to have characteristics of hyperporphyrin spectra. Further deprotonation at much higher basicity makes the optical spectra form three-banded spectra similar to those in the acidic solution. To clarify the molecular origins of these changes, UV-vis, resonance Raman (RR), proton nuclear magnetic resonance (H-1 NMR) experiments are carried out. Our data give evidence that p-OHTPPH2 in DMF can be further deprotonated of pyrrolic-H by higher concentrated NaOH, due to an aprotic medium like DMF effectively weakening the basicity of the porphyrin relative to that of the NaOH, and coordinates with two sodium ions (except the sodium ions that interact with the peripherial phenoxide anions) to form the sodium complexes of p-OHTPPH2 (Na2P, to lay a strong emphasis on the sodium ions that coordinate with the central nitrogen atom), which can be regarded as the porphyrin anions being perturbed by the sodium cations due to their highly ionic character.

Covalent linking of near-infrared luminescent ternary lanthanide (Er3+, Nd3+, Yb3+) complexes on functionalized mesoporous MCM-41 and SBA-15

The near-infrared (NIR) luminescent lanthanide ions, such as Er(III), Nd(III), and Yb(III), have been paid much attention for the potential use in the optical communications or laser systems. For the first time, the NIR-luminescent Ln(dbm)(3)phen complexes have been covalently bonded to the ordered mesoporous materials MCM-41 and SBA-15 via a functionalized phen group phen-Si (phen-Si = 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline; dbm = dibenzoylmethanate; Ln = Er, Nd, Yb). The synthesis parameters X = 12 and Y = 6 h (X denotes Ln(dbM)(3)(H2O)(2)/phen-MCM-41 molar ratio or Ln(dbM)(3)(H2O)(2)/phenSBA-15 molar ratio and Y is the reaction time for the ligand exchange reaction; phen-MCM-41 and phenSBA-15 are phen-functionalized MCM-41 and SBA-15 mesoporous materials, respectively) were selected through a systematic and comparative study. The derivative materials, denoted as Ln(dbM)(3)phen-MCM-41 and Ln(dbm)(3)phen-SBA-15 (Ln = Er, Nd, Yb), were characterized by powder X-ray diffraction, nitrogen adsorption/desorption, Fourier transform infrared (FT-IR), elemental analysis, and fluorescence spectra. Upon excitation of the ligands absorption bands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions.

Memory devices based on lanthanide (SM3+, EU3+, Gd3+) complexes

Memory effects in single-layer organic light-emitting devices based on Sm3+, Gd3+, and Eu3+ rare earth complexes were realized. The device structure was indium-tin-oxide (ITO)/3,4-poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT)/Poly(N-vinyl carbazole) (PVK): rare earth complex/LiF/Ca/Ag. It was found experimentally that all the devices exhibited two distinctive bistable conductivity states in current-voltage characteristics by applying negative starting voltage, and more than 10(6) write-read-erase-reread cycles were achieved without degradation. Our results indicate that the rare earth organic complexes are promising materials for high-density, low-cost memory application besides the potential application as organic light-emitting materials in display devices.

Tuning the saturated red emission: synthesis, electrochemistry and photophysics of 2-arylquinoline based iridium(III) complexes and their application in OLEDs

A series of novel iridium(III) complexes with two 2-arylquinoline derivatives as cyclometalated ligands and one monoanionic ligand, such as acetylacetonate (acac), N,N'-diethyldithiocarbamate (Et(2)dtc) and O,O'-diethyldithiophosphate (Et(2)dtp), as ancillary ligands have been synthesized and structurally characterized by H-1 NMR, MS and elemental analysis (EA). The cyclic voltammetry, absorption, emission and electroluminescence properties of these complexes were systematically investigated. Through extending pi-conjugation, introducing electron-donating groups in the ligand frame, or changing the ancillary ligands, the HOMO energy levels of the iridium(III) complexes can be tuned, while their LUMO levels remain little affected; in consequence, the emission wavelengths of the iridium(III) complexes can be tuned in the range 606-653 nm. The highly efficient organic light-emitting diodes (OLEDs) with saturated red emission have been demonstrated. A maximum current efficiency of 10.79 cd A(-1), at a current density of 0.74 mA cm(-2), with an emission wavelength of 616 nm and Commisioon Internationale de L'Eclairage (CIE) coordinates of (0.65, 0.35), which are very close to the National Television System Comittee (NSTC) standard red emission, have been achieved when using complex (DPQ)(2)Ir(acac) as a phosphor dopant.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Ethylene-propylene copolymerization with bis(beta-enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene-propylene copolymerization, using [(Ph)NC(R-2)CHC(R-1)O](2)TiCl2 (R-1 = CF3, Ph, or t-Bu; R-2 = CH3 or CF3) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High-molecular-weight ethylene-propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R-1 and R-2 influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R-1 and R-2, one complex (R-1 = CF3; R-2 = CH3) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with C-13 NMR to determine the methylene sequence distribution and number-average sequence lengths of uninterrupted methylene carbons.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Interactions of the human telomeric DNA with terbium-amino acid complexes

The human telomeric DNA can form four-stranded structures: the G-rich strand adopts a G-quadruplex conformation stabilized by G-quartets and the C-rich strand may fold into an I-motif based on intercalated C (.) C+ base pairs. There is intense interests in the design and synthesis of compounds which can target telomeric DNA and inhibit the telomerase activity. Here we report the thermodynamic studies of the two newly synthesized terbium-amino acid complexes bound to the human telomeric G-quadruplex and I-motif DNA which were studied by means of UV-Visible, DNA meltings, fluorescence and circular dichroism. These two complexes can bind to the human telomeric DNA and have shown different features on DNA stability, binding stoichiometry, and sequence-dependent fluorescence enhancement. To our knowledge, this is the first report to show terbium-amino acid complexes can interact with the human telomeric DNA.

Syntheses of chromium(III) complexes with Schiff-base ligands and their catalytic behaviors for ethylene polymerization

A series of chromium(III) complexes LCrCl3 (4a-c) bearing chelating 2,2'-iminodiphenyisulfide ligands [L = (2-ArMeC=NAr)(2)S] was synthesized in good yields from the corresponding ligands and CrCl3.(THF). Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display moderate activities towards ethylene polymerization, and produce highly linear polyethylenes with broad molecular weight distribution. Polymer yields, catalyst activities and the molecular weights, as well as the molecular weight distributions of the polymers can be controlled over a wide range by the variation of the structures of the chromium(III) complexes and the polymerization parameters, such as Al/Cr molar ratio, reaction temperature and ethylene pressure.

Novel highly active binuclear neutral nickel and palladium complexes as precatalysts for norbornene polymerization

A series of binuclear neutral nickel and palladium complexes [(XC6H2CH=NC6H3-iPr(2))MRL](2) 4b-f (X=NO2, M=Ni, R=Ph, L=PPh3, 4b; X=H, M=Pd, R=Me, L=PPh3,4c; X=H,M=Pd, R=Me, L=Py, 4d; X=NO2,M=Pd, R=Me, L=PPh3, 4e; X=NO2, M=Pd, R=Me, L=Py, 4f) and [(C10H7CH=NC6H3-iPr(2))MRL](2) 8a-c (M=Ni, R=Ph, L=PPh3, 8a; M=Pd, R=Me, L=PPh3, 8b; M=Pd, R=Me, L=Py, 8c) have been synthesized and characterized. The structures of complexes 4e and 8b have also been confirmed by X-ray crystallographic analysis. With modified methylalummoxane (MMAO) as cocatalysts, these complexes and complex [(C6H3CH=NC6H3-iPr(2))NiPh(PPh3)](2) 4a are capable of catalyzing the addition polymerization of norbomene (NBE) with the high activity up to 2.3 x 10(8) g PNBE/(mol(M) h). The structure of complexes affects considerably catalytic activity towards norbomene polymerization. The polymers obtained with nickel complexes are soluble, while those obtained with palladium complexes are insoluble. Palladium complexes 4c, 4e and 8b bearing PPh3 ligands exhibit much higher activities than the corresponding complexes 4d, M and 8c bearing pyridine ligands under the same conditions.